Production of polymerization products from vinyl ethers



Patented Dec. 28, 1937 PRODUCTION OF POLYMERIZATION PROD- UCTS FROM VINYL ETHEBS Walter-Renae and Otto Schiichting, Lndwigshaten-on-the-Bhine, Germany,

G. Farbenindnstrie on to Aktiengesellscha Frlilkfort-on-the-Main, Germany v No Drawing. Application September.23,,19 3g,

, Serial No.

The present invention relates to the production of polymerization products .i'rom vinyl ethers. .This application is a continuation in] part of our copending application Ser. No. 574,040, flied November 9th l93l.

We have found that polymerization products are obtained in an advantageous manner from vinyl ethers having the general formula in which R is an aliphatic, aromatic or hydroaromatic radicle, and R1, R2 and Ba are hydrogen atoms or aliphatic radicles, by contacting the said vinyl ethers singly, or in admixture with each other, with practically anhydrous inorganic acid reacting condensing agents, as for example tin tetrachloride, stannous chloride, aluminium chloride or sulphate, iron chloride, zinc chloride, boron fluoride, boron hydrogen fluoride, silicon tetrachloride, mercury chloride, sodium bisulphate, potassium bisulphate, alum, sulphuric acid, phosphoric acid hydrochloric acid or hydrofluoric acid. The quantities of the condensing agents employed are generally between 0.001

and 5 per cent of the weight of the vinyl ether employed, but even very small amounts, as for example from 0.001 to 0.5 per cent, of the weight of the vinyl ether employed, of the condensing agents are suflicient inmost cases to eiiect the polymerization. The initial vinyl ethers may be chosen for example from the alkyl, cycloalkyl or aryl ethers of vinyl alcohols, such as methyl-, etlrvb, propyl-, butyl hexylor cyclohexyl, vinyl, propenyl or iso-propenyl ethers and also from the vinyl or alkyl-vinyl ethers of longchain alcohols containing at least 5 carbon atoms, such as alcohols corresponding to the acids containing up to say 35 carbon atoms, es-

pecially of animal and vegetable fats and waxes,

such as octyl, decyl, dodecyl, tetradecyl,

docosanyl or octodecyl alcohols, vinyl ethers of mcntanol and phenyl, eor p-naphthyl or cresyl glycols and of higher glycols, such as of octodecandiol. Besides these vinyl ethers of glycols the vinyl ethers of the mono-alkyl or aryl ethers of glycols may be employed as for example the vinyl ethers of ethylene, or propylene, glycol mono-methyl, -ethyl, -but yi, -phenyl or -cresyl ethers, and the corresponding mono-alkyl or aryl ethers of dior tri-ethylene, or propylene 'glycols.

102,176. In- Germany 4. Claims. (01. zoo-2) this way.

June 2 Specific compounds of these series are for example dior trl-ethylene glycol mono-vinyl ethers, dior trl-ethylene glycol di-vinyl ethers and the corresponding vinyl ethers of l.2-d ior tri-propylene glycols, as well as di-vinyl ether and the di-vinyl ethers of higher glycols as for example o1 octodecandiol.

The polymerization may be carried out with especial advantage by employing the said acid reacting condensing agents deposited or adsorbed on adsorptive materials. When employing polymerizing agents of this kind it is not only possible to polymerize any desired large amount of vinyl ether without the danger of an undue rise of temperature, but it is also possible to separate readily the polymerizing agent employed, which is of great advantage, and, in particular the polymerization temperature can be lowered in As adsorptive substances may be mentioned especially adsorptive hydrosilicates, as for example Florida earth and the adsorptivehydrosilicates obtain'ablein commerce as bleaching earths under the trade names Tonsil, Granosil, Terrana, Isarit or under the' registered trademark T'rankonit, and also active carbon, kieselguhr, pumice, precipitated silica (silicon substratum) or silica gel. Bleaching earths hav-' ing an acid reaction, 1. e. those the aqueous extract ot'which has a pH value of less than '7, as for example the Bavarian bleaching earths obtainable in commerce under the trade names Tonsil HC, Tonsil AC and Granosil, which possess a small content of mineral acid from their production or purification are especially suitable and may be used as such without further impregnation with acid condensing agents.

' The polymerization may be carried out in the liquid, or, with solid condensing agents or condensingagents solidified by deposition on solid carriers, in the gaseous phase. The reaction in the gaseous phase may be effected with the employment of inert gaseous diluents such as carbon dioxide, nitrogen, methane or carbon monoxide. On working in the liquid phase it is preferable to add the condensing agents to the vinyl ethers in small portions, care being taken by cooling for the withdrawal of the heat oi." reaction. The polymerization proceeds very rapidly, especially with strongly acid reacting condensing agents. The polymerization products obtainable are almost colourless or pale yellow to brown products having consistencies ranging from those vents. Also the liquid phase reaction may be of viscous liquids to balsams or soft resins and waxes which dissolve, in the usual organic solthe presence of inert organic diluents as for example liquid or'liquefied aliphatic or aromatic hydrocarbons, such as benzene, toluene, xylene, decahydronaphthalene, saturated ethers, such as diethyl ether, ethyl n-butyl ether, di-n-butyl ether or ethyl propl ether and aliphatic liquid hydrocarbons, such as benzine or like mineral oil fractions, or acetone or esters such as butyl or ethyl acetates.

When carrying out the polymerization it is most advantageous to proceed by first diluting only a small part of the vinyl ether with the solvent, the condensing agent then being added while stirring. The remainder of the vinyl ether is then caused to flow in gradually, care being taken by suitable coolingthat the temperature does not unduly rise, the reaction being generally carried out at from 10 to 120. C., preferably between about 20 and C. When the whole of the vinyl ether has been introduced, the reaction solution may be heated under a refluxcondenser for some time in order to complete the polymerization. The polymerization products obtained after distilling ofi the solvents employed are almost the same as the products obtain ut solvents. The resinous products letWe distillation may be taken up, for example in ethylkether or benzene, and recovered in a pure form after distilling off the solvent employed. As already mentioned mixtures of difierent vinyl ethers may be polymerized, the addition of a small amount of one vinyl ether to a large quantity of another providing a considerable alteration in the properties of a polymerization product obtainable by polymerizing singly the vinyl ether used in preponderating quantity in the mixture as regards mechanical strength and solubility,

On working with solid condensing agents deposited on adsorptive materials it is preferable to work by introducingthe vinyl ether to be polymerized in the gaseous or liquid state at the top of a vertical vessel, capable of being heated and cooled, which is charged with the adsorptive substance serving as the polymerizing agent,

preferably in small quantities mixed with inert filler bodies, such as balls or rings of glass, clay and like inert materials. The polymerization product may be withdrawn from the lower end of the vessel. For the purpose of obtaining a better withdrawal of the reaction heat, especially in the case of the lower members of the series (vinyl methyl ether and vinyl ethyl ether), it is advantageous to work so that the polymerization proceeds incompletely for example by increasing the throughput or adding gaseous inert diluents; in this manner adjustable quantities of vinyl ether leave the reaction space unaltered. The gaseous unchanged vinyl ether leaving the lower end of the vessel together with the polymerization product may be returned'to the vessel again, if necessary after liquefaction, or re-evaporation.

Generally speaking, a more or less vigorous polymerization commences when the vinyl ether is added to the condensing agents deposited on adsorptive substances even at room temperature. When employing less active e. g. very weakly acid condensing agents, as-for example Frankonit S, a slight warming to, say, 40 C. is of advantage. If the reaction be carried out inthe liquid phase in the presence of'a liquid diluent, the reaction temperature may be raised to the boiling point of the diluent;' in this case the vinyl n-butyl ether, only about 1 cubic centimetre of 2,104,001 carried out in order to render it less vigorous, in.

ether to be polymerized is advantageously gradually added to the diluent which is kept boiling and contains the polymerizing agent suspended therein. On working in the vaporous phase temperatures up to 250 Q. 'may be ap- 5 plied but the reaction is preferably carried out also in this case at a temperature of from 40 to 100 C. in the reaction space.

The resulting polymerization products are more or less viscous liquid, or solid, saturated 5 substances depending on the natureof the ether employed and on the degree of polymerization and are stable to dilute aqueous acids and alkalies. They may be employed, for coating and adhesive purposes, as substitutes for oils in oil- 15 filled subsoil or submarine cables and as resins in the production of artificial masses, the products may also be applied as intermediate layers for compound glass; they can be further em ployed as softening and plasticizing agents for 0 India rubber and rubber-like polymerization products of diolefines such as butadiene or isoprene, or for masses from polymerized styrene.

The vinyl ethers, especially in large amounts, can be polymerized particularly rapidly but 25 without danger of an undue rise of temperature by employing boron halides and boron halide hydrogen halides as for example boron fluoride, chloride or bromide, or boron hydrogen fluoride, in the form of their addition or conversion prod- 30 ucts with organic oxygen bearing compounds as for example ethers, such as diethyl or dibutyl ether, ketones or alcohols (see Gmelinfs Hand- .buch der anorganischen Chemie, 8th edition, volume Boron, page 114 et seq.) as the condens ing agents.

For the purpose of accurate dosing of the condensing agent, the addition or conversion products of the boron halides are advantageously employed only in very dilute solutions, as for example about 2 per cent solutions. The alcohols or ethers employed for the preparation of the said addition products may be employed as solvents for the said compounds. The amounts of boron halide addition products necessary for the polymerization are extremely small and frequently amount to only about 0.001 per cent of the vinyl ether to be polymerized. Thus for example for the polymerization of a litre of vinyl 50 a 2 per cent solution of the addition product of boron fluoride with di-n-butyl ether (which can be prepared by introducing a current of boron fluoride into an equi-molecular proportion of di-n-butyl ether 'at about 10 ,C.) in di-n-butyl ether is necessary Also this polymerization of the vinyl ethers may be carried out in the pres-. ence of a solvent for the vinyl ether, as for example in the presence of saturated ethers or of hydrocarbons of the aliphatic, hydroaromatic or 60 aromatic series, but an advantage of this modification is that substantial quantities of solvents for the vinyl ether are not necessary.

The properties of the polymerization products obtainable in this manner are very similar to 65 those of the products obtained as hereinbefore described by means of the other said acid condensing agents; they may, however, be obtained in an entirely colourless form. As the last traces of the vinyl ether are only polymerized with difliculty, the productaflrst obtained are in'some cases still unsaturated to a slight extent. After being allowed to stand for some time or after removing the last traces of nonpolymerized vinyl ether in vacuo, the polymerization products be- 75 The most satisfactory temperatures for the polymerization of the vinyl ethers when employ- 0 between about 80 ing addition products of boron halides he between about40 and 60 C. The polymerization may be carried out, however, at the lower or higher temperatures already mentioned. The polymerization may be eilected in open vessels provided with reflux condensers or in closed vessels under pressure.

Bart oi the lower mem ers oi the new poly merizedv ethers according to the present invention is soluble in water as for example the polymeric vinyl methyl ether, the vinyl ether of diethylene glycol mono-ethyl ether and the vinyl ether oi ethylene glycol mono-ethyl ether, the first mentioned compound preferably, however, with the conjoint employment of a dissolution assistant suchas methyl or ethyl alcohols or ethylene glycol mono-methyl ether; these compounds may find useful application in sizing ori dressing. e higher members vinyl ether, are K generally easily soluble iii gasoline, benzene, turpentine oil and like solvents for waxes.

The following examples will iurther illustrate how this invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

The monomeric vinyl ethers used as terials for the manufacture of polymerizates may known method, but are preferably prepared by the method of U. S. P. 1,959,927, according to which acetylene is caused to act at temperatures C. and about 250 C. on liquefied organic, monomeric (non-polymerized) hydroxy compounds.

Example 1 initial mao.25 part of stannous chloride is added to so parts of vinyl-n-butyl ether (CHa=CHO--'C4Ha,

which may be prepared by heating anhydrous n-butanol with vinyl chloride at C. in an autoclave in the presence of metallic sodium) in a reaction vessel provided with a wide reflux condenser. After a few mi utes the temperature begins to rise and at a temperature of about 45 to 50 C. sudden boiling with a consequent rapid rise in temperature to C. takes place. The reaction product is a yellowish brown balsamlike mass which is purified by steam distillation. 35 parts of a viscous liquid yellow polymerization product are obtained.

Tin tetrachloride or aluminium chloride may be employed instead of stannous chloride.

Example 2 i partof'aluminium chloride is suspended in 200 partsof dry benzene and then 200 parts of vinyl ethyl ether (Cl-lz=CH--O- Czl-la) are added to the suspension while stirring. About 20 parts of the vinyl ether are added at once in order to start the reaction, the remainder being added a little at atime. The occurrence of turbidity indicates the commencement of the polymerization. When the temperature has risen to from 60 to 80 C., the vinyl ether is added in portions oi from 1 to 2 parts, whereby the fact that the reand this procedure ether, 144 parts or a yellow are obtained.

such as the polymeric octodecyl white, waxy bodies which are the presentbe made according to any balsam remains behind,

action is taking place may be detected not only by a rise. in temperature but also by a brown colouration oithe mass, which disappears after the reaction. when the colouration has disappeared, further amountsoi vinyl ether are added, is repeated. When all the vinyl ether has been introduced, the whole is stirred for an hour at 80 C. The volatile constituents are distilled oi! irom the resulting mixture with steam and the residue is taken up with ethyl ether. Alter drying'and distilling oil the balsam-like product Example 3 20 parts or ethyl-n-propenyl ether (CH3\-CH=CHO-C2H5) are gradually introduced into a mixture of 1 part of tin tetrachloride and 80 parts of benzene. The temperature rises to-the boiling point of. the benzene and the reaction mixture assumes a brown colour. en the whole of the ether has been -introduced, the benzene and volatile constituents are expelled with steam. The residue is taken up with ether, and the ethereal solution is' shaken up with animal charcoal and filtered.

soft resin remains behind.

Example 4 aluminium chloride is suspended in benzene, 50 parts of ethyl-isopropenyl benzene and the reaction mixture assumes a brownish red colour. After distilling ed the After distilling 0d the ethena brownish yellow,

1 part or l50flparts of ether benzene and volatile constituents with steam, a

mass resembling a vegetable the behaviour of which towards. solvents is generally speaking the same as the polymerization product obtained from vinyl ethyl ether.

brown, very sticky Example 5 I 14 parts of vinyl ortho-cresyl ether.

' ethyl alcohol to C. in an autoclave) are allowed to drop gradually into a suspension of 0.3 part of aluminium chloride in 40,.parts of benzene, whereby the polymerization commences with the evolution of much heat and the forma-- tion of a'red colouration. The diluent and the volatile constituents are distilled oil with steam and-after cooling, the water is poured ofi from the residue. The reaction product is a violet coloured brittle resin which is soluble in ethyl ether, acetone, 06 per cent ethyl alcohol, butyl acetate and hydrocarbons of the benzene series but which is scarcely soluble in benzine.

If vinyl phenyl ether be employed instead of vinyl ortho-cresylether, a solid red polymerization product is obtained which. is soluble only with diillculty in the said solvents with the exception of acetone in, which it dissolves readily.

Example 8 50 parts of vinyl meta-cresyl ether are allowed to stand at room temperature after the addition or 5 parts of zinc chloride. After having been allowed to stand for 2 day the original readily mobile liquid has beenconverted into a colourless, balsam-like, very sticky resin. The polymerization product is readily soluble in ethyl ether, acetone, butyl acetate and benzene but difliculty soluble in ethyl alcohol and benzine.

If the polymerization be carried out at higher temperatures, as for example at from to C. a polymerization of the same intensity is attained after from 1 to 2 hours; the resulting prodnot has a slightly greenish shade, however.

Example 7 parts of vinyl ethyl ether are introduced into a vessel provided device, a cooling jacket and a reflux condenser. The ether is warmed to 35 C. and 0.5 part or a 2 per cent solution of the addition product of boron fluoride and di-n-butyl ether (which boils at C.) in di-n-butyl ether is added. 2000 parts of vinyl ethyl ether are allowed to flow in at into the stirring vesseldescribed in Example 7 and, after warming to 40 C., 0.5 part of a 2 per cent solution of the addition product of boron fluoride and di-ethyl ether in di-ethyl ether is added. The temperature or the polymerization which soon commences is kept at about 40 to 50 C. partly by cooling and partly by the addition of further amounts of vinyl-n-butyl ether cooled to a temperature of 15 C. In this manner about 2000 parts of vinyl butyl ether and a further 3.5 parts of the solution of the boron fluoride addition product are added in the course of 2 hours. After stirring for about a further 2 hours, the polymerization is practically completed. The last traces of non-polymerized vinyl butyl ether are polymerized after allowing the reaction mixture to stand for several days at room temperature 'or slightly elevated about 40 C. A colourless, honey-like highly viscous and sticky product is obtained.

In the same manner vinyl cyclohexyl ether may be polymerized by substituting the aforesaid quantity of vinyl butyl ether by the same quantity of the cyclohexyl ether.

Example 9 100 parts 'of vinyl methyl ether and 1 part of with an efilcientstirring product is quite stable to brotemperatures, as for exampleceeds. the temperature oi the contents of the vessel gradually rises from 9C. (the boiling point or vinyl methyl ether) to about 20 C. 1000 parts or vinyl methyl ether are then added at about 20 C. during the course 01"4 hours while 1 part of the solution 01' the said polymerizing agent is gradually added at the same time. The contents of the vessel are then heated to 30 C. until a sample withdrawn and dissolved in cyclohexane only absorbs small amounts of bromine. Remainders oi non-polymerized vinyl methyl ether are removed from the polymerization product by distillation in vacuo at about 200 millimetres of mercury.

The resulting polymerization product is easily soluble in organic solvents such as aliphatic alcohols, ketones, esters or acids and in hydrocarbons and is miscible with water in any desired proportion. In the latter case it is. however, advantageous to employ a dissolution assistant such as methyl or ethyl alcohols, ethylene glycol mono- Example 10 I 200 parts of. vinyl octodecyl ether obtainable from octodecyl alcohol and acetylene at from about 160 to C. in the presence of a small quantity of caustic potash, are fused in a stirring vessel. 0.6 part'of the solution of polymerizing agent specified in Example 7 is added at 50 immediately commences is kept at a temperature of from 50 to 60 C. by cooling. 2000 parts of vinyl octodecyl ether together with 2.5 parts of the said solution of the polymerizing agent are gradually added during the course of 3 hours. The resulting saturated, solid polymerization product melts at 55 C. and resembles in its appearance colourless translucent paraflln wax.

In the same manner octyl, decyl, dodecyl and tetradecyl ethers of vinyl alcohol as well as the vinyl ethers of oleic alcohol and of the alcohols corresponding tovthe acids of Montan wax can be polymerized. If desired, a 2 per cent solution of boron fluoride in acetic acid may be employed as polymerizing agent.

Example 11 10 parts of octodecan -diol divinyl ether (C1aH3s(O--CH=CH2) 2) obtainable by acting with perature of from 160 to 180 C. in the presence 01' 2 per cent of caustic potash on octodocan -diol (obtainable by catalytic hydrogenation of castor oil at a temperature of from 230 to 250 C. under a pressure of hydrogen of about 100 atmospheres), are dissolved in 800 parts ethyl ether.

100 parts of the solution obtained are introduced into an enamelled vessel provided with an eflicient stirring device, a cooling jacket and a reflux condenser. The solution is warmed to boiling (about 36 proportion with the formation 01 C. and the vigorous reaction which acetylene at a temof vinyl C.) and 0.6 part of a 1 per 75 I I I cent solution of the addition product of. boron v ized vinyl ethyl ether, if such be still present, are

removed by distillation in vacuo at about 100 millimetres oi mercury.

The polymerization'product obtained is very tenacious and stringy and resembles. synthetic rubber; in contrast to the product obtained according to Example '7 it is insoluble in organic solvents such as aliphatic, cyclo-aliphatic and aromatic hydrocarbons, as for example benzine, cyclohexane, benzene, ethyl alcohol or acetone, but swells therein. a a

' Example 12 An internally enamelled vertically arranged tubular reaction vessel having a sheet metal jacket capable of being heated, is filled with glass beads of about 1 centimetre diameter to each litre of which 50 cubic centimetres of the bleaching earth obtainable in ,commerce under the trade name "Granosil" are uniformly added. The temperature in the vessel is kept at about 70 C. by means of hot water circulating in the heating Jacket. The supply pipe from a storage. vessel for vinyl ether and an outlet pipe are led through the closure at the upper end of the vessel. Non-polymerized vaporous vinyl ethyl ether escapes through the said outlet, is liquefied in a condenser arranged above the said storage vessel and is supplied to the said vessel again. The

- heat of polymerization oi the vinyl ether is to a large extent withdrawn by the heat required for evaporating the non polymerized fraction of the vinyl ether. A vessel-for collecting the polymerization product is arranged in an airtight manner at the bottom of the reaction vessel.

About 500 grams of liquid vinyl ethyl ether per 'hourand-per litre of reaction space are supplied to the reaction chamber from the storage vessel: about 150 grams of polymerizationproduct are obtained while the non-polymerized vinyl ethyl standing for some time.

ether passes back into the storage vessel again bywayoi the condenser. The resulting polymerization product, which generally still contains small amounts of non polymerized ether dissolved therein, becomes quite inert to bromine after It a further purification be desired, the polymerization. product may be redissolved in a suitable solvent, such as ben- Zeno or cyclohexane.

A similar result is obtained when gaseous vinyl ethyl ether is introduced, the polymerization product and ;the non-polymerized vinyl ethyl ether are withdrawn from the lower end of the tube and the non polymerized vinyl ethyl ether is separated and led in again in the vapour phase.

Example-13 filled with "Granosil'? and glass beads asde-' scribed-in Example 12. The polymerized vinyl butyl ether is withdrawn from the lower end of I .the reaction vessel and becomes quite stable to bromine after standing for sometime.

Example 14 r parts of the divinylethe'r' oi octodecandiol are dissolved in 1000 parts of benzene or benzine and 0.5 part of a 1 per cent solution of boron fluoride in ,di-n-butyl ether are added. The reac tion mixture grows warm and viscous and solidifies to a solid jelly, from which. the benzene or benzine can be removed by pressing. A similar product can be obtained from the divinyl ether of tri-ethylene glycol Y Example 15 0.6 part of a 2 per cent solution of the doubleobtainable by acting with acetylene on diethylene glycol mono-ethyl ether in the presence of 2 per cent, by weight of the latter, of anhydrous caustic potash) in a stirring vessel. In the course of about 1 hour 900-parts of the aforesaid vinyl ether are slowly introduced while stirring and keepingthe temperature at. from 40 to 50 C.

by cooling. The reaction mixture is then stirred at the said temperature until the product does not react with bromine any more which effect is usually attained after from 3 to 4; hours. The resulting colourless and highly viscous polymerization product is miscible with water in any proportion.

. Example 16 0.05 part oi.v a 2 per cent solution of the double compound of boron fluoride and di-butyl ether in di-butyi ether is added to 5 parts or di-vinyl ether (CH:=CHO-CH=CH:). With a slight evolution otheat the whole solidifies to a solid,

brittle mass.

What we claim-is:

1. From-viscous liquid to solid amorphous polymeric vinyl ethers, the monomers of which correspond to the general formula R1 Rs 11/ o-R in which R denotes a cyclic hydrocarbon radical selected from the aryl and cycloalkyl radicals, and R1. R2 and R: stand for a member of the group consisting of hydrogen and the alkyl radicals, the said polymeric ethers being saturated substances practically inert to bromine and stable to dilute aqueous acids and alkalis.

2. The polymeric vinyl phenylether, which is a from viscous liquid to solid amorphous saturated substance practically inert to bromine and stable to dilute aqueous acids and alkalis.

3. The polymeric vinyl cresyl ether, which is a from viscous liquid to solid amorphous saturated substance practically inert to bromine and stable-to dilute aqueous acids and alkalis.

4. The polymeric vinyl cyclohexyi ether, which is a from viscous liquid to solid amorphous saturated substance practically inert to bromine and stable to dilute aqueous acids and alkalisi WALTER REPPEQ O'I'ID BCHLICHTING. 

